US3974120A - Fluorosilicone copolymers and process for the preparation thereof - Google Patents

Fluorosilicone copolymers and process for the preparation thereof Download PDF

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Publication number
US3974120A
US3974120A US05/574,331 US57433175A US3974120A US 3974120 A US3974120 A US 3974120A US 57433175 A US57433175 A US 57433175A US 3974120 A US3974120 A US 3974120A
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copolymer
cyclic
sub
aprotic solvent
mol
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US05/574,331
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English (en)
Inventor
John S. Razzano
Verne G. Simpson
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General Electric Co
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General Electric Co
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Priority to US05/574,331 priority Critical patent/US3974120A/en
Priority to DE2618852A priority patent/DE2618852C2/de
Priority to GB17646/76A priority patent/GB1540876A/en
Priority to JP51050044A priority patent/JPS51134796A/ja
Priority to FR7613331A priority patent/FR2310373A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C08G77/08—Preparatory processes characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups

Definitions

  • the present invention relates to a process for producing fluorosilicone copolymers from mixtures of fluoroalkyl cyclotrisiloxanes and, more specifically, to the production of such copolymers from mixtures of (i) cyclic trisiloxanes wherein at least one of the organo groups attached to the silicon atom is trifluoropropyl with (ii) a second trisiloxane co-monomer.
  • a copolymer of less than 90 mol % of trifluoropropylsiloxy groups should be more efficient in use of fluorosilicone groups than a blend of a 90 mol % fluorosilicone copolymer and a dimethylsiloxy polymer at the same fluorosilicone content.
  • trifluoropropyl substituted tricyclic monomers do not readily copolymerize in the desired composition range. See Johannson and, also Bostick, U.S. Pat. No. 3,337,497, the latter disclosing that fluorine substitution on alkyl should be avoided in producing ordered copolymers from cyclic trisiloxanes.
  • the present invention involves dissolving a fluorosilicone cyclic siloxane trimer and organosiloxane cyclic trimer in certain aprotic solvents, such as tetrahydrofuran, and polymerizing the solution with certain non-equilibrating catalysts such as organolithium in the temperature range of 0°C. to 150°C., limited by solution reflux temperatures, for times of 5 minutes to a number of hours.
  • aprotic solvent such as tetrahydrofuran
  • aprotic solvents such as tetrahydrofuran, dimethylsulfoxide, tetramethylurea, hexamethyl phosphoric triamide, dioxane, and the like, have the ability to enhance the activity of catalysts such as butyl lithium, as is well known. This is fortunate, since certain preferred aprotic solvents, such as tetrahydrofuran, do not boil at high enough temperatures for butyl lithium to be effective if this promotion effect did not occur.
  • the amount of aprotic solvent used in the polymerization of the cyclotrisiloxanes is determined primarily by the ratio of the cyclic trimers.
  • Another object of the present invention is to provide trifluoropropyl organopolysiloxane copolymer oils and gums having a viscosity from 100,000 to 200,000,000 centipoise at 25°C., having enhanced resistance to swelling by hydrocarbon fluids, by a process comprising copolymerization of cyclic trisiloxanes in admixture with alkyl lithium catalysts and an aprotic solvent.
  • a further object of the present invention to provide trifluoroalkyl organopolysiloxane copolymer oils or gums having a viscosity from 100,000 to 200,000,000 centipoise at 25°C., wherein the fluoroalkylsiloxane co-monomer comprises 40 to 85 mol % of the copolymer units.
  • the present invention provides a process for producing diorganopolysiloxane copolymers having a viscosity of from 100,000 to 200,000,000 centipoise at 25°C. comprising (a) forming an admixture of
  • R is methyl, ethyl, vinyl or phenyl
  • R is, independently, as defined above, (i) being present in an amount of from 40 to 85 mol % of the total of (i) and (ii), (iii) is from 5 to 300 parts per million of an alkyl lithium catalyst, the alkyl component containing from 1 to 12 carbon atoms, and (iv) an aprotic solvent, said aprotic solvent being capable of dissolving both of the trimers (i) and (ii) and the copolymer product; (b) reacting said admixture at a temperature between 0°C. and 150°C. to form said copolymer; and (c) recovering said copolymer from the reaction mixture.
  • a preferred embodiment comprises recovering the product by stripping the solvent from the copolymer. It is preferred to deactivate the catalyst, e.g., by adding a drop of acetic acid prior to stripping.
  • the stripping can be carried out at any conventional temperature, e.g., 50°C. to 200°C., at atmospheric pressure or under a vacuum of, e.g., 1 to 100 mm. of Hg, depending on the solvent.
  • the copolymerization reaction will usually require from 1/2 hour to 96 hours and, more usually, from 50 minutes to 10 hours.
  • the cyclic trimer co-monomers (i) and (ii) are known in the art, see, e.g., the Johannson and Bostick patents cited above.
  • the amount of co-monomer (i) in admixture with (ii) will vary between 40 and 85 mol %. Most preferably, however, (i) will comprise from 50 to 75 mol % of the total of (i) and (ii).
  • the R substituent radicals in the above formulae of the trisiloxanes is CH 3 , i.e., methyl.
  • the process provides diorganopolysiloxane copolymer oils or gums of from 30 to 200,000,000 centipoise viscosity at 25°C. depending on whether or not, for example, a conventional chain-stopper is employed.
  • cyclotrisiloxanes (i) and (ii) which can be employed in the practice of the present invention can be varied widely.
  • cyclic trisiloxanes can be mentioned, for example, 2,4,6-trimethyl-2,4,6-tris(3,3,3-trifluoromethylpropyl) cyclotrisiloxane, hexamethylcyclotrisiloxane, hexaphenylcyclotrisiloxane, cis- or trans-2,4,6-trimethy;-2,4,6-triphenylcyclotrisiloxane, various isomers of trimethyltriethylcyclotrisiloxane, and the like.
  • the alkyl group in the alkyl lithium catalyst is generally monovalent hydrocarbon straight chain or branched, of 1 to 8 carbon atoms such as methyl, ethyl, propyl, heptyl, isooctyl, and the like; or cycloalkyl of 4 to 8 carbon atoms, such as cyclohexyl, cycloheptyl, and the like. These are commercially available or can be readily obtained by known methods.
  • the preferred catalyst is butyl lithium.
  • non-acid oxygen-containing and nitrogen-containing organic solvents capable of coordinating with the lithium.
  • these include, for instance, tetrahydrofuran (hereinafter referred to as "THF"), tetrahydropyran, diethoxyethane, dimethyl ether of diethylene glycol, dimethyl acetamide, N-methyl pyrrolidone, dimethyl sulfoxide, dioxane, diethyl ether of diethylene glycol, various tertiary amines such as, for instance, dimethyl aniline, tributyl amine, pyridine, etc.
  • THF tetrahydrofuran
  • tetrahydropyran diethoxyethane
  • diethoxyethane dimethyl ether of diethylene glycol
  • dimethyl acetamide dimethyl acetamide
  • N-methyl pyrrolidone dimethyl sulfoxide
  • dioxane diethyl ether of diethylene glycol
  • Solvents which contain active hydrogen or an acid hydrogen should be avoided because of the reactivity of the lithium with the acidic hydrogen to produce new reaction centers and thereby causing a decrease in yield or an increase in the number of undesirable by products contrary to the intent of this invention.
  • the preferred aprotic solvents are tetrahydrofuran, dimethyl sulfoxide, tetramethyl urea, hexamethylphosphoric triamide and dioxane.
  • the cyclic polysiloxanes, (i) and (ii), above are placed in a vessel, along with solvent (iv).
  • copolymerization will begin. Specifically, there will be used 5 to 300 parts per million and, preferably, 10 to 100 parts per million, of the alkyl lithium catalyst.
  • the copolymerization will be carried out at a temperature of from 0° to 150°C. and more preferably, at a temperature of 50° to 100°C. If a temperature below 0° or above 150°C. is used, then the maxiumm yield of diorganopolysiloxane copolymer is not achieved and, below 0°C., the polymerization rate is somewhat too slow.
  • the mixed cyclic siloxane of Formulaes (i) and (ii) above, and the catalysts are heated or cooled to the indicated temperature range for from 5 minutes to 100 hours, preferably, 50 minutes to 10 hours, during which time copolymerization is completed. At this point, there will be 80 to 95% by weight or more of the cyclic siloxanes converted to the desired diorganopolysiloxane copolymer oil or gum. In this case, there will be 5 to 20% of the cyclic polysiloxanes of Formulae (i) and (ii) in the equilibrated mixture. At this point, the product can be recovered. For example, a few drops of acetic acid are added and the solvent is stripped.
  • the viscosity of the copolymer can be controlled by adding a chain-stopper, to the mixture of co-monomers (i) and (ii), catalyst (iii) and (iv).
  • chain-stoppers can be, for example, disiloxanes or low molecular weight diorganopolysiloxanes having triorganosiloxy terminal units, that is, having monofunctional terminal units.
  • the organo substituents in such chain-stoppers are typically alkyl of 1 to 8 carbon atoms, vinyl, phenyl or cycloalkyl of 4 to 8 carbon atoms. Also, they can comprise haloalkyl of from 1 to 8 carbon atoms, such as trifluoropropyl.
  • the amount of chain-stopper that is used in the mixture will be selected to produce the desired final molecular weight or viscosity of the diorganopolysiloxane copolymer oil or gum. Small amounts, e.g., 0.01 ml. of chainstopper per 100 ml. of mixed trimers will produce higher molecular weights, e.g., 100,000 centipoise at 25°C. The highest molecular weights will be obtained without chain-stoppers.
  • the process of this invention produces linear trifluoropropylorganopolysiloxane copolymer oils or gums.
  • the copolymer oils or gums can be formulated, e.g., by mixing with fillers, such as fumed silica or precipitated silica; extending fillers, such as zinc oxide, iron oxide, titanium oxide, diatomaceous earth, and the like; heat aging additives, such as iron oxide; pigments, and other additives, such as flame retardents, for instance, platinum, by itself, or in combination with other materials and self-bonding additives, such as for instance, triallylisocyanurate.
  • fillers such as fumed silica or precipitated silica
  • extending fillers such as zinc oxide, iron oxide, titanium oxide, diatomaceous earth, and the like
  • heat aging additives such as iron oxide
  • pigments, and other additives such as flame retardents, for instance, platinum, by itself, or in combination with other materials and self-bonding additives,
  • the copolymer gums can be mixed into a uniform mass to which is added a curing agent, e.g., a peroxide curing agent, such as benzoyl peroxide or dicumyl peroxide.
  • a curing agent e.g., a peroxide curing agent, such as benzoyl peroxide or dicumyl peroxide.
  • the resulting composition can be cured at elevated temperatures, e.g., from 100 to 300°C., or they can be cured by radiation to produce a silicone copolymer elastomer.
  • the oils can be used as plasticizers, in greases, and as de-foamers.
  • a resin flask is placed 49.45 g. of a mixture of (i) 16.76 g. of 1,3,5-trimethyltris-1,3,5-(3,3,3-trifluoropropyl)-cyclotrisiloxane and (ii) 7.96 g. of trimethylcyclotrisiloxane, (i) being present in an amount of 50 mol % of the mixture of (i) and (ii), and 24.73 g. of dry tetrahydrofuran (iv).
  • the flask is purged with dry nitrogen for 30 minutes to dry the mixtures of cyclic polysiloxanes to a level of less than 10 parts per million of water.
  • the flask is heated to reflux in an oil bath and 10 microliters of butyl lithium in the form of a 15% solution in heptane, is added.
  • the reaction is allowed to continue for 20 minutes and a gum is formed and stirring is stopped. At the end of 2 hours, the product is a firm gum.
  • the product is taken up in 100 ml. of ethyl acetate and allowed to stand for 16 hours.
  • An additional 80 ml. of ethyl acetate is added and the solution is run into 1600 ml. of methanol.
  • the precipitated polymer is separated by decantation and air-dried for 16 hours. Final drying produces a copolymer having methyl,3,3,3-trifluoropropyl siloxane and dimethyl siloxane units, 23 g., 93% yield.
  • Example 1 The procedure of Example 1 is repeated, using 40 mol % of (i) in the mixture of (i) and (ii). A high yield of oil resistant copolymer is obtained, after adding one drop of acetic acid and stripping of the solvent at 80°C. and 10 mm. of Hg. l
  • Example 2 The procedure of Example 2 is repeated, using 85 mol % of (i) in the mixture of (i) and (ii). A high yield of oil resistant copolymer is obtained.
  • the above detailed description is seen to provide a simple and straight-forward procedure for producing low molecular weight and high molecular weight diorganopolysiloxane copolymer oils and gums from trifluoropropyl cyclic trisiloxanes.
  • the copolymer gums may be advantageously used to produce silicone elastomers having outstanding properties such as, for instance, increased resistance to degradation by oil, as compared to silicone elastomers formed from diorganopolysiloxane gums where the organo groups are mostly composed of low molecular weight and aromatic substituent groups such as methyl or vinyl.
  • the oils are useful as plasticizers, grease components, and the like.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Silicon Polymers (AREA)
US05/574,331 1975-05-05 1975-05-05 Fluorosilicone copolymers and process for the preparation thereof Expired - Lifetime US3974120A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US05/574,331 US3974120A (en) 1975-05-05 1975-05-05 Fluorosilicone copolymers and process for the preparation thereof
DE2618852A DE2618852C2 (de) 1975-05-05 1976-04-29 Verfahren zum Herstellen von Diorganopolysiloxan-Copolymeren
GB17646/76A GB1540876A (en) 1975-05-05 1976-04-30 Fluorosilicone copolymers
JP51050044A JPS51134796A (en) 1975-05-05 1976-05-04 Process for preparing fluorosilicone copolymer
FR7613331A FR2310373A1 (fr) 1975-05-05 1976-05-05 Procede de fabrication de copolymeres de fluorosilicones

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US05/574,331 US3974120A (en) 1975-05-05 1975-05-05 Fluorosilicone copolymers and process for the preparation thereof

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JP (1) JPS51134796A (enExample)
DE (1) DE2618852C2 (enExample)
FR (1) FR2310373A1 (enExample)
GB (1) GB1540876A (enExample)

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4089833A (en) * 1977-05-02 1978-05-16 General Electric Company Process aids for fluorosilicone polymers
FR2464276A1 (fr) * 1979-08-30 1981-03-06 Gen Electric Stoppeur de chaine issu d'une reaction de mise en equilibre entre un fluorosilicone et un polydimethylsiloxane, et son procede de preparation
FR2469423A1 (fr) * 1979-11-09 1981-05-22 Gen Electric Procede de preparation d'un fluide de fluorosilicone a terminaisons silanol
US4317899A (en) * 1978-11-13 1982-03-02 General Electric Company Process for producing fluorosilicone polymers
US4348531A (en) * 1979-08-30 1982-09-07 General Electric Company Fluorosilicone polydimethylsiloxane equilibration chainstopper and process for manufacture
FR2503725A1 (fr) * 1981-04-09 1982-10-15 Gen Electric Composition de caoutchouc de silicones durcissables
US4499229A (en) * 1983-04-01 1985-02-12 General Electric Company One package, stable, moisture curable, alkoxy-terminated organopolysiloxane compositions
US4683277A (en) * 1986-07-02 1987-07-28 Dow Corning Corporation Method for preparing vinyl terminated fluorine-containing polydiorganosiloxane
GB2234517A (en) * 1989-07-28 1991-02-06 Dow Corning Silethynyl-siloxane copolymers and method of making them
EP0338577A3 (en) * 1988-04-22 1991-03-06 Chisso Corporation Organosiloxane and process for preparing the same
EP0428958A3 (en) * 1989-11-20 1991-11-21 General Electric Company Polar aprotic catalysts for formation of fluorosilicone fluids
EP0429928A3 (en) * 1989-11-20 1991-11-27 General Electric Company Polar aprotic catalysts for formation of fluorosilicone fluids
US5140087A (en) * 1988-04-22 1992-08-18 Chisso Corporation Organosiloxane and process for preparing the same
EP0563902A1 (en) * 1992-03-31 1993-10-06 Dow Corning Toray Silicone Company, Limited Fluorosilicone block copolymers and method for the preparation thereof
US5696219A (en) * 1997-01-21 1997-12-09 Dow Corning Corporation Silyl ester initiators for cyclosiloxane ring opening polymerization
US5824736A (en) * 1992-09-21 1998-10-20 Dow Corning Toray Silicone Co., Ltd. Fluorosilicone rubber composition
US5830969A (en) * 1997-05-28 1998-11-03 Dow Corning Corporation Silyl ester initiators for ring opening polymerization of cyclosiloxanes
US5853617A (en) * 1997-05-14 1998-12-29 Gallagher; Christopher T. Method and composition for suppressing oil-based foams
US20080146717A1 (en) * 2005-01-17 2008-06-19 Pieter Gijsman Heat Stabilized Moulding Composition
US20080167390A1 (en) * 2006-06-01 2008-07-10 James Archer Defoamer composition for suppressing oil-based and water-based foams
US20080269429A1 (en) * 2007-04-27 2008-10-30 Gelest, Inc. Low molecular weight siloxanes with one functional group
US20110040063A1 (en) * 2009-08-14 2011-02-17 Shin -Etsu Chemical Co., Ltd. Preparation of triorganosiloxy end-capped organopolysiloxane

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Publication number Priority date Publication date Assignee Title
JPS5628219A (en) * 1979-08-17 1981-03-19 Asahi Glass Co Ltd New fluorine-containing elastomer
WO1994005749A1 (en) * 1992-09-09 1994-03-17 Lord Corporation High strength, low conductivity electrorheological materials
GB2278846B (en) * 1993-06-10 1997-04-16 Gen Electric Fluorosilicone terpolymeric fluid
US6056976A (en) * 1998-11-12 2000-05-02 Leiras Oy Elastomer, its preparation and use
JP5338380B2 (ja) * 2008-12-02 2013-11-13 信越化学工業株式会社 オルガノポリシロキサン及びその製造方法並びにフルオロシリコーンゴム組成物

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US3483270A (en) * 1966-04-11 1969-12-09 Gen Electric Stereospecific organosiloxane-macromolecular hydrocarbon block copolymers

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FR1226739A (fr) * 1958-04-07 1960-07-15 Dow Corning Fluides fluoroalkylsiloxanes
US3122521A (en) * 1960-03-18 1964-02-25 Dow Corning Method of polymerizing fluoroalkyl-substituted cyclotrisiloxanes
DE1495501B2 (de) * 1963-03-25 1971-11-18 Dow Corning Corp , Midland, Mich (V St A ) Polymerisationskatalysatoren fuer cyclische organosilicium verbindungen
US3249585A (en) * 1964-04-29 1966-05-03 Dow Corning Preparation of siloxanes with sih bonds with an alkyl lithium catalyst
US3503926A (en) * 1968-05-17 1970-03-31 Dow Corning Solid lubricant composition
BE756725A (fr) * 1969-09-29 1971-03-29 Dow Corning Procede de preparation de 3,3,3-trifluoropropylmethylpolysiloxanes

Patent Citations (1)

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US3483270A (en) * 1966-04-11 1969-12-09 Gen Electric Stereospecific organosiloxane-macromolecular hydrocarbon block copolymers

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4089833A (en) * 1977-05-02 1978-05-16 General Electric Company Process aids for fluorosilicone polymers
US4317899A (en) * 1978-11-13 1982-03-02 General Electric Company Process for producing fluorosilicone polymers
FR2464276A1 (fr) * 1979-08-30 1981-03-06 Gen Electric Stoppeur de chaine issu d'une reaction de mise en equilibre entre un fluorosilicone et un polydimethylsiloxane, et son procede de preparation
US4348531A (en) * 1979-08-30 1982-09-07 General Electric Company Fluorosilicone polydimethylsiloxane equilibration chainstopper and process for manufacture
FR2469423A1 (fr) * 1979-11-09 1981-05-22 Gen Electric Procede de preparation d'un fluide de fluorosilicone a terminaisons silanol
FR2503725A1 (fr) * 1981-04-09 1982-10-15 Gen Electric Composition de caoutchouc de silicones durcissables
US4499229A (en) * 1983-04-01 1985-02-12 General Electric Company One package, stable, moisture curable, alkoxy-terminated organopolysiloxane compositions
US4683277A (en) * 1986-07-02 1987-07-28 Dow Corning Corporation Method for preparing vinyl terminated fluorine-containing polydiorganosiloxane
EP0338577A3 (en) * 1988-04-22 1991-03-06 Chisso Corporation Organosiloxane and process for preparing the same
US5140087A (en) * 1988-04-22 1992-08-18 Chisso Corporation Organosiloxane and process for preparing the same
GB2234517A (en) * 1989-07-28 1991-02-06 Dow Corning Silethynyl-siloxane copolymers and method of making them
US5102968A (en) * 1989-07-28 1992-04-07 Dow Corning Limited Method of making silethynyl-siloxane copolymers
GB2234517B (en) * 1989-07-28 1992-12-09 Dow Corning Silethynyl-siloxane copolymers and method of making them
EP0428958A3 (en) * 1989-11-20 1991-11-21 General Electric Company Polar aprotic catalysts for formation of fluorosilicone fluids
EP0429928A3 (en) * 1989-11-20 1991-11-27 General Electric Company Polar aprotic catalysts for formation of fluorosilicone fluids
US5300609A (en) * 1992-03-31 1994-04-05 Dow Corning Toray Silicone Co., Ltd. Fluorosilicone block copolymers
EP0563902A1 (en) * 1992-03-31 1993-10-06 Dow Corning Toray Silicone Company, Limited Fluorosilicone block copolymers and method for the preparation thereof
US5824736A (en) * 1992-09-21 1998-10-20 Dow Corning Toray Silicone Co., Ltd. Fluorosilicone rubber composition
US5696219A (en) * 1997-01-21 1997-12-09 Dow Corning Corporation Silyl ester initiators for cyclosiloxane ring opening polymerization
US5853617A (en) * 1997-05-14 1998-12-29 Gallagher; Christopher T. Method and composition for suppressing oil-based foams
US5830969A (en) * 1997-05-28 1998-11-03 Dow Corning Corporation Silyl ester initiators for ring opening polymerization of cyclosiloxanes
US8772394B2 (en) * 2005-01-17 2014-07-08 Dsm Ip Assets B.V. Heat stabilized moulding composition
US20080146717A1 (en) * 2005-01-17 2008-06-19 Pieter Gijsman Heat Stabilized Moulding Composition
US8969460B2 (en) 2005-01-17 2015-03-03 Dsm Ip Assets B.V. Heat stabilized moulding composition
US20080167390A1 (en) * 2006-06-01 2008-07-10 James Archer Defoamer composition for suppressing oil-based and water-based foams
EP1985645A3 (en) * 2007-04-27 2008-11-26 Gelest, Inc. Low molecular weight siloxanes with one functional group
US20100298591A1 (en) * 2007-04-27 2010-11-25 Gelest, Inc. Asymmetric low molecular weight siloxanes with one functional group
US8455599B2 (en) 2007-04-27 2013-06-04 Gelest Technologies, Inc. Asymmetric low molecular weight siloxanes with one functional group
US7799888B2 (en) 2007-04-27 2010-09-21 Gelest, Inc. Low molecular weight siloxanes with one functional group
US20080269429A1 (en) * 2007-04-27 2008-10-30 Gelest, Inc. Low molecular weight siloxanes with one functional group
US20110040063A1 (en) * 2009-08-14 2011-02-17 Shin -Etsu Chemical Co., Ltd. Preparation of triorganosiloxy end-capped organopolysiloxane
US8110646B2 (en) * 2009-08-14 2012-02-07 Shin-Etsu Chemical Co., Ltd. Preparation of triorganosiloxy end-capped organopolysiloxane

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Publication number Publication date
FR2310373A1 (fr) 1976-12-03
JPS618095B2 (enExample) 1986-03-12
DE2618852A1 (de) 1976-11-18
GB1540876A (en) 1979-02-21
FR2310373B1 (enExample) 1981-08-21
DE2618852C2 (de) 1984-10-04
JPS51134796A (en) 1976-11-22

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